|Publication number||US6128924 A|
|Application number||US 09/115,775|
|Publication date||Oct 10, 2000|
|Filing date||Jul 14, 1998|
|Priority date||Jul 19, 1996|
|Also published as||DE69725725D1, DE69725725T2, DE69725725T3, EP0912452A1, EP0912452B1, EP0912452B2, US5824127, WO1998003442A1|
|Publication number||09115775, 115775, US 6128924 A, US 6128924A, US-A-6128924, US6128924 A, US6128924A|
|Inventors||James C. Bange, William G. Dorfeld, James C. Hayes, Josef C. Lapp|
|Original Assignee||Corning Incorporated|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (21), Non-Patent Citations (16), Referenced by (70), Classifications (16), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
______________________________________SiO2 60-73 MgO 0-5Al2 O3 8-14 CaO 1-13B2 O3 5-17 SrO 0-8TiO2 0-5 BaO 0-14Ta2 O5 0-5______________________________________
This is a division of application Ser. No. 08/742,610, filed Oct. 28, 1996, now U.S. Pat. No. 5,824,127 issued Oct. 20, 1998.
This application claims the benefit of U.S. Provisional Application No. 60/022,193, filed Jul. 19, 1996.
This invention is directed to arsenic-free glass compositions and methods of making such glasses which are suitable for use as substrates in flat panel display devices without having to use arsenic containing materials.
Liquid crystal displays (LCDs) are passive flat panel displays which depend upon external sources of light for illumination. They are manufactured as segmented displays or in one of two basic configurations. The substrate needs (other than being transparent and capable of withstanding the chemical conditions to which it is exposed during display processing) of the two matrix types vary. The first type is intrinsic matrix addressed, relying upon the threshold properties of the liquid crystal material. The second is extrinsic matrix or active matrix (AM) addressed, in which an array of diodes, metal-insulator-metal (MIM) devices, or thin film transistors (TFTs) supplies an electronic switch to each pixel. In both cases, two sheets of glass form the structure of the display. The separation between the two sheets is the critical gap dimension, of the order of 5-10 μm.
Intrinsically addressed LCDs are fabricated using metal deposition techniques, typically at temperatures ≦350° C., followed by standard metal etching procedures. As a result, the substrate requirements therefor are often the same as those for segmented displays. Soda-lime-silica glass with a barrier layer has proven to be adequate for most needs. A high performance version of intrinsically addressed LCDs, the super twisted nematic (STN) type, has an added requirement of extremely precise flatness for the purpose of holding the gap dimensions uniform. Because of that requirement, soda-lime-silica glass made using the float glass manufacturing process must be polished. Such polishing processes are expensive and time consuming, and generate a large amount of glass particles which have the potential to negatively impact further processing of the glass sheets. Alternatively, glass can be formed using a process which does not require polishing, e.g. fusion downdraw.
Extrinsically addressed LCD's can be further subdivided depending upon the nature of the electrical switch located at each optical element (subpixel). Two of most popular types of extrinsically (or active matrix, AMLCD) addressed LCD's are those based on either amorphous (a-Si) or polycrystalline (poly-Si) silicon thin film transistors (TFT's).
U.S. Pat. No. 4,824,808 (Dumbaugh, Jr.) lists four desirable properties for a glass to exhibit in order to fully satisfy the needs of a substrate for extrinsically addressed LCD's:
First, the glass must be essentially free of intentionally added alkali metal oxide to avoid the possibility of alkali metal contamination of the TFT;
Second, the glass substrate must be sufficiently chemically durable to withstand the reagents used during the manufacture of the TFT;
Third, the expansion mismatch between the glass and the silicon present in the TFT array must be maintained at a relatively low level even as processing temperatures for the substrates increase; and
Fourth, the glass must be capable of being produced in high quality thin sheet form at low cost; that is, it must not require extensive grinding and polishing to secure the necessary surface finish.
That last requirement is most difficult to achieve inasmuch as it demands a sheet glass production process capable of producing essentially finished glass sheet. A process capable of meeting this requirement is a particular downdraw process known as the overflow downdraw, or fusion, sheet manufacturing process. The overflow downdraw process is described, for example, in U.S. Pat. No. 3,338,696 (Dockerty) and U.S. Pat. No. 3,682,609 (Dockerty). Fusion formed glass sheets, unlike float glass sheets, are sufficiently flat that they do not need to be polished after forming. Two glasses which meet the above requirements, Corning Incorporated Codes 7059 and 1737 sheet glass, are currently employed as substrates for extrinsically addressed LCD's. These glasses are made using the overflow downdraw process, and hence do not require polishing after forming.
Recent improvements in the resolution of extrinsically addressed LCD's have led to the development of a fifth glass requirement, that is, a high glass strain point. This property is used as an indication of the thermal shrinkage of the glass. As can be appreciated, the lower the strain point, the greater is this thermal shrinkage. Low thermal shrinkage is desirable for precise alignment during successive photolithographic and other patterning steps during the TFT processing. Consequently, glasses having higher strain points are generally preferred for extrinsically addressed LCD's, particularly those which employ poly-Si TFT technology. Thus, there has been considerable research to develop glasses demonstrating high strain points so that thermal shrinkage is minimized during device processing. Corning Code 1737 glass, which has the highest strain point (666° C.) in the AMLCD substrate industry, is rapidly becoming an industry standard. Concurrent with their high strain points, these glasses often have high melting temperatures, e.g. on the order of 1550-1650° C.
Another technology termed "chip-on-glass" (COG) has further emphasized the need for the substrate glass to closely match silicon in thermal expansion. Thus, the initial LCD devices did not have their driver chips mounted on the substrate glass. Instead, the silicon chips were mounted remotely and were connected to the LCD substrate circuitry with compliant or flexible wiring. As LCD device technology improved and as the devices became larger and required finer resolutions, these flexible mountings became unacceptable, both because of cost and of uncertain reliability. This situation led to Tape Automatic Bonding (TAB) of the silicon chips. In that process the silicon chips and electrical connections to the chips were mounted on a carrier tape, that subassembly was mounted directly on the LCD substrate, and thereafter the connection to the LCD circuitry was completed. TAB decreased cost while improving reliability and increasing the permitted density of the conductors to a pitch of approximately 200 μm--all significant factors. COG, however, provides further improvement over TAB with respect to those three factors. Hence, as the size and quality requirements of LCD devices increase, COG is demanded for those devices dependent upon the use of integrated circuit silicon chips. For that reason, the substrate glass preferably demonstrate a linear coefficient of thermal expansion closely matching that of silicon; i.e., a linear coefficient of thermal expansion (0°-300° C.) between about 32-46×10-7 /° C., most preferably 32-40×10-7 /° C.
Many of the glasses manufactured for flat panel display applications, particularly those which are formed by downdraw processes (e.g., the fusion or slot draw processes), are melted or formed using manufacturing equipment comprised of refractory metals, e.g. platinum or platinum alloys, particularly in the fining and conditioning sections of the process, where refractory metals are employed in order to minimize the creation of compositional in homogenieties and gaseous inclusions caused by contact of the glass with oxide refractory materials. In addition, many of these manufacturing processes employ arsenic as a fining agent. This is because arsenic is among the highest temperature fining agents known, meaning that, when added to the molten glass bath, it allows for O2 release from the glass melt even at high melting temperatures (e.g. above 1450° C.). This high temperature O2 release, (which aids in the removal of gases during the melting and fining stages of glass production), coupled with a strong tendency for O2 absorption at lower conditioning temperatures, (which aids in the collapse of any residual gaseous inclusions in the glass), results in a glass product essentially free of gaseous inclusions. In addition, the oxidizing nature of the arsenic fining package allows for protection of the platinum based metal systems by preventing contamination as a result of tramp metals reduction. Other fining agents typically melt and release their oxygen far too early when added as fining agents to high melting temperature glasses and reabsorb O2 too late during the conditioning process, thereby disabling their fining abilities. From an environmental point of view, it would be desirable to find alternative methods of making such high melting point and strain point glasses without having to employ arsenic as a fining agent. It would be particularly desirable to find methods for making such glasses via downdraw (especially fusion-like) processes. Unfortunately, previous efforts at doing so have been hindered by the production of unacceptable amounts of bubbles in the glass. This has been a particular problem with glasses which employ refractory metals such as platinum or platinum containing alloys in their molten glass delivery systems. This is because platinum can cause an electrochemical reaction to occur with the glass which results in bubble formation on or near the platinum (commonly referred to as blistering) contacting region of the glass.
We have found that by maintaining a low amount of water in the glass during the glass forming process, other fining constituents which are normally less efficient at high melting temperatures (melting temperature is defined herein as the temperature at which the glass exhibits a viscosity of 200 poise), e.g. Sb2 O3, CeO2, SnO2, Fe2 O3, and mixtures thereof, can be employed if needed in place of As2 O3 to facilitate successful fining of the glass. Maintaining a low amount of water in the glass thus enables the formation of high melting point glasses (ie., glasses wherein the temperature at which the viscosity corresponds to 200 poise is greater than about 1500° C.) which are essentially or substantially arsenic-free. By substantially arsenic-free it is meant that such glasses have less than 0.02 mole percent As2 O3 (such amounts are normally present as a result of raw material impurity). The invention also enables the formation of such high melting point glasses using manufacturing systems which employ platinum or platinum containing alloys which contact the glass during the melting or forming steps of the manufacturing process. These methods are particularly suited for forming glasses which are formed using a downdraw process, such as, for example, Corning Code 1737.
One manner of measuring the water content in the glass is by measuring beta-OH (β-OH). β-OH, as used herein, is a measure of the hydroxyl content in the glass as measured by IR spectroscopy, and is determined using the fundamental hydroxyl absorption, which for this material occurs at about 2809 nm. The β-OH is the linear absorption coefficient (absorbance/mm thickness) of the material at 2809 nm. The equation below shows how β-OH is calculated from the sample's IR transmittance spectrum.
β-OH=(1/X) LOG10 (T1 /T2)
where X is the sample thickness in millimeters, T1 is the sample transmittance at the reference wavelength (2600 nm) and T2 is the minimum sample transmittance of the hydroxyl absorption wavelength (2809 nm). The reference wavelength compensates for signal loss due to surface reflections, scatter, and refraction in the sample, and is chosen from a region of no absorption and as close as possible to the absorption wavelength of interest.
In a preferred embodiment of the present invention for forming low arsenic containing glasses via a downdraw sheet forming process, the batch constituents are selected so that the resultant glass has a water content therein, as indicated by β-OH level, which is less than 0.5, preferably less than 0.45, more preferably less than 0.4, and most preferably less than 0.35.
Preferably, the glasses formed in accordance with the invention are formed using less than 0.1 mole percent As2 O3, and most preferably are essentially free of As2 O3 in the resultant glass. We have found that silicate glasses (especially aluminosilicate and borosilicate glasses) formulated to result in such β-OH values in the resultant formed glass can be fined using less than 0.02 mole percent As2 O3, expressed as the amount of As2 O3 present in the resultant glass. Even when formed using a downdraw process employing a platinum based metal delivery system, such glasses can be formed without any significant amounts of electrochemical blistering occurring. In the most preferred embodiment, in order to facilitate fining of these glasses, Sb2 O3, CeO2, SnO2, Fe2 O3, and mixtures thereof are added to such glasses, alone or in combination, in an amount between about 0.02-2 mole percent. In a preferred embodiment, Sb2 O3 is added in an amount between about 0.2-0.5 mole percent.
The water content or β-OH value of the glass can be reduced in a variety of ways. For example, simply by appropriate selection of batch materials, the water level in the glass can be adjusted to some extent. Further water reduction can be achieved by adding drying agents, such as halide materials. For example, halide containing materials may be added in an amount which results in the final glass having a composition between about 0.1 to 4 mole percent halide, more preferably 0.1 to 2 mole percent halide, and most preferably about 0.1 percent halide. In a preferred embodiment for forming the glass composition disclosed in the example, 0.4 mole percent chlorine is batched, e.g. as CaCl2, resulting in about 0.15 to 0.19 mole percent Cl in the resultant glass.
Additionally, it is desirable to keep the sum of the partial pressures of all dissolved volatile gases below 1 atmosphere. One method of facilitating this result is by limiting the amount of sulfur in the resultant glass by appropriate selection of batch materials. Preferably, selection of batch materials should be made so that the sulfur, expressed as SO3, in the resultant formed glass is as low as possible, preferably less than 100 ppm, more preferably less than 50, and most preferably less than 25 ppm.
The methods in accordance with the present invention are useful for forming silicates containing large amounts of Al2 O3 and B2 O3, e.g., glasses having 60-77 mole percent SiO2, 8-14 mole percent Al2 O3, and 5-17 mole percent B2 O3.
The methods in accordance with the present invention are particularly advantageous in forming high strain point aluminoborosilicate glasses such as, for example, those having a composition, expressed in terms of mole percent on the oxide basis, of
______________________________________SiO2 60-73 MgO 0-5Al2 O3 8-14 CaO 1-13B2 O3 5-17 SrO 0-8TiO2 0-5 BaO 0-14Ta2 O5 0-5______________________________________
More preferably, the base glass has a composition, expressed in terms of mole percent on the oxide basis, of
______________________________________SiO2 64-70 MgO 0-5Al2 O3 9.5-14 CaO 3-13B2 O3 5-12 SrO 0-5.5TiO2 0-5 BaO 2-8Ta2 O5 0-5 MgO + CaO + SrO + BaO 10-20______________________________________
With the exception of the low water content, glasses within this preferred composition range are disclosed, for example, in U.S. Pat. No. 5,374,595, the specification of which is hereby incorporated by reference. Preferred glasses formed in accordance with the present invention exhibit linear coefficients of thermal expansion over the temperature range of 0°-300° C. between 32-46×10-7 /° C., more preferably between 32-40×10-7 /° C., strain points higher than 630° C., more preferably higher than 640° C., and most preferably greater than 650° C. liquidus temperatures less than 1125° C., liquidus viscosities which are sufficient to enable formation by a downdraw manufacturing process, preferably greater than 400,000, and more preferably greater than 600,000 poises (60,000 Pa.s), a weight loss of less than 2 mg/cm2 after immersion for 24 hours in an aqueous 5% by weight HCl solution at 95° C., long term stability against devitrification at melting and forming temperatures, and melting viscosities of about 200 poises (20 Pa.s) at less than 1675° C. The methods of the present invention may be employed in glasses having compositions within the boundaries set forth above, such as, for example, glasses listed as examples in U.S. Pat. No. 5,374,595, thereby enabling such glasses to be fined and formed without having to use arsenic.
In the most preferred glasses, in addition to the low water level, the level of Al2 O3 will exceed that of B2 O3 and in the most preferred glasses the composition will consist essentially, expressed in terms of mole percent, of about
______________________________________SiO2 65-69 MgO 1-5Al2 O3 10-12 CaO 3-9B2 O3 7-10 SrO 1-3TiO2 0-3 BaO 2-5Ta2 O5 0-3 MgO + CaO + SrO + BaO 11-16______________________________________
Preferably, the ratio Al2 O3 :B2 O3 in such glasses is greater than 1.
The invention thus enables the formation of silicate sheet glasses having high melting points (greater than 1500° C.), as well as the formation of silicate sheet glasses using manufacturing processes which employ refractory metals such as molybdenum and platinum in their forming regions. Forming region, as used herein, refers to the portion of the manufacturing process prior to which the final form of the glass is imparted to the glass, and includes the melting, conditioning, and fining portions of the manufacturing process.
FIG. 1 illustrates a humidity controlled enclosure for use in accordance with the present invention.
The present invention relates to silicate glass compositions and methods of making such silicate glass compositions while employing little or no arsenic. The preferred glasses are aluminosilicate or borosilicate glasses. The preferred manufacturing processes for such glasses is via a downdraw sheet manufacturing process. As used herein, downdraw sheet manufacturing process refers to any form of glass sheet manufacturing process in which glass sheets are formed while traveling in a downward direction. In the fusion or overflow downdraw forming process, molten glass flows into a trough, then overflows and runs down both sides of a pipe, fusing together at what is known as the root (where the pipe ends and the two overflow portions of glass rejoin), and is drawn downward until cool. The overflow downdraw sheet manufacturing process is described, for example, in U.S. Pat. No. 3,338,696 (Dockerty) and U.S. Pat. No. 3,682,609 (Dockerty). One advantage to the fusion forming process is that the glass sheet can be formed without the glass surface contacting any refractory forming surfaces. This provides for a smooth, contaminant-free surface. In addition, this technique is capable of forming very flat and thin sheets to very high tolerances. Consequently, fusion formed glass sheets, unlike float glass sheets, do not require costly polishing steps for TFT and STN LCD applications.
Other forms of downdraw sheet forming techniques include the slot draw and redraw forming techniques. In the slot draw technique, molten glass flows into a trough having a machined slot in the bottom. The sheets of glass are pulled down through the slot. The quality of the glass is obviously dependent on the accuracy of the machined slot. Redraw processes generally involve preforming a glass composition into a block of some shape, then reheating and drawing the glass downwardly into a thinner sheet product.
The glasses of the present invention preferably have less than 0.2 mole percent As2 O3, more preferably less than 0.1 mole percent As2 O3, and most preferably less than 0.02 mole percent As2 O3 (an amount which is normally present as a result of raw material impurity).
It is believed that the method described herein are applicable to a wide variety of glasses, particularly those formed via downdraw manufacturing processes which employ platinum in their forming regions. Application of the invention to Corning Code 1737 glass, for example, is demonstrated as follows, with reference to Table I below. These glasses were prepared in a laboratory-scaled continuous melting unit similar to the overflow downdraw melting units typically used for commercial production of this type of product. This experimental melting unit employs a platinum/rhodium alloy refractory metal delivery system, wherein the molten glass contacts the platinum alloy metal. Example 4 of Table I corresponds closely to commercially available Corning Code 1737 glass, and was fined accordingly using an amount of arsenic which resulted in about 0.4 mole percent being present in the resultant glass. Examples 1, 2, and 3 illustrate the effect that decreasing amounts of water has on these compositions. As the β-OH values of the glass decrease, so do the gaseous inclusions (Inc./lb.) in glass. In these examples, gaseous inclusions are primarily a result of electrochemical blistering caused by the platinum alloy pipes which deliver the molten glass, and consequently accurately mimic the manufacturing processes employing metals such as platinum. Gaseous inclusions were measured on a per pound basis over a period of two to three days. As illustrated by the examples, the inclusions per pound dropped significantly with each decrease of β-OH value. The fact that this was done without having to use As2 O3 as a fining agent makes this accomplishment significant.
Table I records similar glass compositions of varying β-OH levels, expressed in terms of parts by weight on the oxide basis, illustrating the invention. Inasmuch as the sum of the individual constituents totals or very closely approximates 100, for all practical purposes the reported values may be deemed to represent weight percent. Table IA records the same glass compositions expressed in terms of mole percent on the oxide basis. The actual batch ingredients may comprise any materials, either oxides or other compounds, which, when melted together with the other batch components, will be converted into the desired oxide in the proper proportions. For example, SrCO3 and CaCO3 can provide the source of SrO and CaO, respectively. In Example 3, Cl was added as CaCl2 at a level of 0.2 weight percent in excess of the batch, resulting in about 0.087 weight percent Cl retained in the resultant glass. About 2.7 weight percent water in excess of the batch was added to Examples 1 and 4.
Table I also lists measurements of several chemical and physical properties determined on the glasses in accordance with techniques conventional in the glass art. Thus, the linear coefficient of thermal expansion (CTE) over the temperature range 0E-300° C. expressed in terms of X10-7 /° C., and the softening point (S.P.), annealing point (A.P.), and strain point (St.P.) expressed in terms of ° C., were determined by fiber elongation. The durability (HCl Dur.) in HCl was determined by measuring the weight loss (mg/cm2) after immersion in a bath of aqueous 5% by weight HCl at 95° C. for 24 hours.
The liquidus temperatures (Liq. Temp.) of the glasses were measured using the standard liquidus method, which involves placing crushed glass particles in a platinum boat, placing the boat in a furnace having a region of gradient temperatures, heating the boat in an appropriate temperature region for 24 hours, and determining by means of microscopic examination the highest temperature at which crystals appear in the interior of the glass. The melting temperature (M.P., in ° C.) (defined as the temperature at which the glass melt demonstrates a viscosity of 200 poises [20 Pa.s]) was calculated employing the Fulcher equation as fit to the high temperature viscosity data. The liquidus viscosity (Liq. Vis.) was also calculated using the Fulcher equation coefficients, and is expressed in terms of X1,000,000 poises (100,000 Pa.s). SnO2 was added to examples 1-3 in an amount suitable to replicate melting conditions in production, wherein the tin electrodes employed in melting the glass result in residual tin oxide in the resultant glass.
TABLE I______________________________________ 1 2 3 4______________________________________SiO2 59.49 58.82 58.91 57.07Al2 O3 16.4 16.7 16.58 16.46B2 O3 8.29 8.3 8.21 8.35MgO 0.737 0.739 0.765 0.77CaO 4.109 4.111 4.116 4.21SrO 1.889 1.883 1.887 1.88BaO 8.6 8.59 8.61 9.49SnO2 0.062 0.09 0.092Sb2 O3 1.857 1.852 1.856 0As2 O3 0 0 0 1.11% Added H2 O 2.70 0 0 2.7Cl 0 0 0.087 0#OH 0.481 0.41 0.358 0.440Inc./lb. 15.2 2.06 0.26 0.21S.P. 973 976 977 968M.P. 1641 1638 1644 1625St.Pt. 660 665 664 658A.P. 717 719 720 714Liq. Temp. 1080 1080 1090 1050Liq. Vis. 1.37 1.4 1.06 2.51HCl Dur. 0.46 0.44 0.45 0.61CTE 36.3 36.6 36.6 37.6______________________________________
TABLE IA______________________________________ 1 2 3 4______________________________________SiO2 68.6 68.2 68.3 67.3Al2 O3 11.1 11.4 11.3 11.4B2 O3 8.25 8.31 8.22 8.5MgO 1.27 1.28 1.32 1.35CaO 5.08 5.11 5.11 5.32SrO 1.26 1.27 1.27 1.28BaO 3.89 3.9 3.91 4.39SnO2 0.03 0.04 0.04 --Sb2 O3 0.44 0.44 0.44 --As2 O3 -- -- -- 0.4______________________________________
These examples, which are meant to be illustrative and not limiting, demonstrate that aluminoborosilicate glasses such as those falling within the compositional ranges described above can be made using downdraw manufacturing processes.
In a preferred embodiment of the invention, the glass is formed in a manufacturing system which employs platinum, molybdenum, palladium, rhodium or an alloy thereof in contacting relationship with the glass, and the partial vapor pressure of hydrogen outside this portion of the manufacturing system relative to the partial vapor pressure of hydrogen in the glass or inside that manufacturing vessel. The partial pressure of hydrogen outside the vessel can be controlled, for example, by enclosing part of the vessel in an enclosure, and varying the partial pressure of hydrogen, or the dew point, inside the enclosure as desired. By so controlling the relative partial pressures of hydrogen inside versus outside the platinum or molybdenum containing portion of the glass manufacturing system, we can control, and if desired, reduce the amount of surface blisters which were heretofore problematic in such glass manufacturing systems which employed platinum or molybdenum. The partial vapor pressure of hydrogen inside and outside the system can be controlled, for example, by controlling the partial vapor pressure of water inside and outside the system. The desired relative partial pressures inside versus outside the forming vessels depends upon whether the forming vessel contains platinum or molybdenum (or palladium or rhodium) as a glass contacting material.
For example, platinum is desirable for use in glass forming vessels primarily because of its inert properties. However, platinum enables hydrogen migration to occur from the glass melt through the platinum, thereby creating an oxygen rich layer at the glass/platinum interface which results in surface blisters. Consequently, for the platinum glass manufacturing vessels, it is most desirable to maintain the relative inside and outside partial pressures of hydrogen to be substantially equal, so that no migration of hydrogen, either in or out of the glass manufacturing vessel, occurs. However, if any migration is to occur, it is more desirable that it occur from the outside in, and thus in another embodiment the partial pressure of hydrogen outside the platinum or molybdenum manufacturing vessel is maintained at a higher level then is present inside the vessel.
On the other hand, molybdenum acts as a reducing material toward oxide melts. Therefore it is desirable to maintain a partial pressure of hydrogen outside the molybdenum containing forming vessel which is lower than that inside the forming vessel, to reduce the amount of blisters formed as a result of reduction of the glass constituents (e.g. formation of SO2 bubbles as a result of reduction of dissolved SO3).
In another preferred embodiment, a measurement device is used to measure the relative partial pressures of hydrogen inside versus outside the manufacturing vessel, and the humidity or dew point outside the vessel is then controlled accordingly. A preferred such measurement apparatus is shown in FIG. 1. Platinum vessel 10 includes platinum walls 12 through which molten glass 13 is flowing. The platinum walls 12 of vessel 10 can have any shape (e.g. round or rectangular in cross-section), and the direction of flow of the molten glass through vessel 10 is not important. A platinum flag electrode 14 is immersed into the molten glass. By platinum flag, it is meant a flat sheet of platinum, so that the both sides of the platinum contact the molten glass, and therefore the flag does not experience hydrogen permeation. Also immersed into the molten glass 13 is a platinum tube 20, the interior of which is in contact with the atmosphere outside platinum vessel 10. Both flag electrode 14 and the platinum tube 20 are isolated from the platinum manufacturing vessel 10 via an insulating material 24. The flag electrode 14 and platinum tube 20 are then connected as illustrated in FIG. 1. Controller 15 is used to adjust the voltage from variable d.c. power source 16 necessary to maintain the target potential between electrodes 14 and 20. The current necessary to sustain this voltage is then read from ammeter 17 as an indicator of the flow of hydrogen through the platinum wall 20, and thus platinum wall 12 as well. For example, an increase in current indicates a net decrease in the rate of hydrogen migration out of the glass and into the atmosphere outside the Pt system. Conversely, a decrease in current would indicate a net increase in the rate of hydrogen migration out of the glass and into the atmosphere.
The apparatus illustrated in FIG. 1 is enclosed by enclosure 30 (shown schematically), which enables the control of the partial pressure of hydrogen surrounding the platinum vessel 10. Thus, if the measurement system described above indicates a change from the target potential, the humidity inside enclosure 30 can be adjusted to correct for this change. Other variations within the scope of the claimed invention will be apparent to those skilled in the art. For example, the potential between flag 14 and platinum tube 20 could be monitored simply by a voltage regulator, and a signal produced relative to the voltage measured, the signal then being sent to a control device capable of increasing or decreasing the humidity or dew point in the enclosure in response to the signal. In addition, while in FIG. 1, only a portion of the vessel 10 is enclosed, in a preferred embodiment the entire portion of the manufacturing process employing platinum vessels is enclosed. Clearly, a similar control system can be devised if the partial pressure of hydrogen is varied directly.
Such control of the relative partial pressures of hydrogen, as well as the measuring device described above, are explained in more detail in U.S. patent application Ser. No. 08/736,848, now U.S. Pat. No. 5,824,127, the specification of which is hereby incorporated by reference.
Although the invention has been described in detail for the purpose of illustration, it is understood that such detail is solely for that purpose and variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention which is defined by the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2009764 *||Jan 15, 1934||Jul 30, 1935||Corning Glass Works||Fining heat absorbing reduced glasses|
|US2982053 *||Nov 19, 1956||May 2, 1961||Corning Glass Works||Method of removing dissolved water from 96 percent silica glass|
|US3338696 *||May 6, 1964||Aug 29, 1967||Corning Glass Works||Sheet forming apparatus|
|US3673049 *||Oct 7, 1970||Jun 27, 1972||Corning Glass Works||Glass laminated bodies comprising a tensilely stressed core and a compressively stressed surface layer fused thereto|
|US3682609 *||Oct 6, 1969||Aug 8, 1972||Corning Glass Works||Controlling thickness of newly drawn glass sheet|
|US3849097 *||Mar 27, 1972||Nov 19, 1974||Corning Glass Works||Method for continuously hot forming strong laminated bodies|
|US3850602 *||Dec 18, 1972||Nov 26, 1974||Heraus Schott Quarzschmelze||Salt vapor atmosphere treatment of quartz crystal granules|
|US4018965 *||Apr 14, 1975||Apr 19, 1977||Corning Glass Works||Photochromic sheet glass compositions and articles|
|US4824808 *||Nov 9, 1987||Apr 25, 1989||Corning Glass Works||Substrate glass for liquid crystal displays|
|US4870034 *||Jul 5, 1988||Sep 26, 1989||Schott Glaswerke||Borosilicate glass|
|US5374595 *||Nov 22, 1993||Dec 20, 1994||Corning Incorporated||High liquidus viscosity glasses for flat panel displays|
|US5508237 *||Aug 10, 1994||Apr 16, 1996||Corning Incorporated||Flat panel display|
|US5688300 *||Feb 9, 1996||Nov 18, 1997||Corning Incorporated||Conveying glass tubing|
|US5785726 *||Oct 28, 1996||Jul 28, 1998||Corning Incorporated||Method of reducing bubbles at the vessel/glass interface in a glass manufacturing system|
|US5824127 *||Oct 28, 1996||Oct 20, 1998||Corning Incorporated||Arsenic-free glasses|
|EP0527320B1 *||Jul 2, 1992||Oct 9, 1996||Corning Incorporated||Flat panel display device comprising a strontium aluminosilicate glass substrate|
|EP0528114A1 *||May 14, 1992||Feb 24, 1993||Corning Incorporated||Flat panel display comprising an alkaline earth aluminoborosilicate glass substrate|
|EP0528149B1 *||Jul 2, 1992||Oct 11, 1995||Corning Incorporated||Flat panel display device comprising an alkaline earth aluminoborosilicate glass substrate|
|EP0538568A1 *||Aug 7, 1992||Apr 28, 1993||Corning Incorporated||Lead silicate glasses|
|EP0607865A1 *||Jan 13, 1994||Jul 27, 1994||Corning Incorporated||High liquidus viscosity glasses for flat panel displays|
|GB1147830A *||Title not available|
|1||*||Boff e et al., Formation of Bubbles During Devitrification and Remelting of Crystals in Glass, Nucleation and Crystallization Symposium, pp. 47 54.|
|2||Boffe et al., "Formation of Bubbles During Devitrification and Remelting of Crystals in Glass," Nucleation and Crystallization Symposium, pp. 47-54.|
|3||Budd et al., "The Formation of Gas Bubbles in Glass at High Temperature," Glass Technology, 3:124-129, Aug. 1962.|
|4||*||Budd et al., The Formation of Gas Bubbles in Glass at High Temperature, Glass Technology , 3:124 129, Aug. 1962.|
|5||de Kever et al., "Influence of batch moisture and atmosphere on the melting behavior of As2 O3 - and Sb2 O3 -containing glasses," Glastechnische Berichte, Feb. 1992, pp 64-66.|
|6||*||de Kever et al., Influence of batch moisture and atmosphere on the melting behavior of As 2 O 3 and Sb 2 O 3 containing glasses, Glastechnische Berichte, Feb. 1992, pp 64 66.|
|7||Eagan et al., "Bubble Formation in Glass by Reaction with Silicon and Silicon-Germanium Alloys," Sandia Laboratories, Sep. 2, 1992, pp. 300-301.|
|8||*||Eagan et al., Bubble Formation in Glass by Reaction with Silicon and Silicon Germanium Alloys, Sandia Laboratories, Sep. 2, 1992, pp. 300 301.|
|9||Fenstermacher et al., "A Study of Water Content of Container Glasses," Sep. 1965, The Glass Industry, pp. 518-521.|
|10||*||Fenstermacher et al., A Study of Water Content of Container Glasses, Sep. 1965, The Glass Industry , pp. 518 521.|
|11||Firth et al., "The Effect of Moisture on the Melting, Working, and other Properties of Potash-Lead Oxide-Silica Glasses of the `English Crystal` Type," Journal of the Society of Glass Technology, 1926, vol. X, pp. 220-229.|
|12||*||Firth et al., The Effect of Moisture on the Melting, Working, and other Properties of Potash Lead Oxide Silica Glasses of the English Crystal Type, Journal of the Society of Glass Technology , 1926, vol. X, pp. 220 229.|
|13||H. Scholze, "Gases and Water in Glass," Lectures on Glass and Technology, Rensselaer Polytechnic Institute, Mar. 30-Apr. 1, 1996.|
|14||*||H. Scholze, Gases and Water in Glass, Lectures on Glass and Technology, Rensselaer Polytechnic Institute, Mar. 30 Apr. 1, 1996.|
|15||J. P. Poole, "Fundamentals of Fining," Commission on Glass, Annual Meeting, Toronto, Canada, 1969, pp. 169-176.|
|16||*||J. P. Poole, Fundamentals of Fining, Commission on Glass, Annual Meeting, Toronto, Canada, 1969, pp. 169 176.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6468933||Sep 21, 1999||Oct 22, 2002||Nippon Electric Glass Co., Ltd.||Alkali-free glass and method of producing the same|
|US6642163||Dec 20, 2001||Nov 4, 2003||Nippon Electric Glass Co., Ltd.||CRT funnel of a non beam-index type|
|US6754429||Jun 25, 2002||Jun 22, 2004||Corning Incorporated||Method of making optical fiber devices and devices thereof|
|US6990285||Jul 31, 2003||Jan 24, 2006||Corning Incorporated||Method of making at least one hole in a transparent body and devices made by this method|
|US6993936||Sep 4, 2003||Feb 7, 2006||Corning Incorporated||System and method for suppressing the formation of oxygen inclusions and surface blisters in glass sheets and the resulting glass sheets|
|US7000432||Mar 7, 2002||Feb 21, 2006||Asahi Glass Company, Limited||Process for producing a glass for cathode ray tubes|
|US7006228||Jun 24, 2003||Feb 28, 2006||Corning Incorporated||Methods for quantifying the oxidation state of glass|
|US7032412||Mar 13, 2003||Apr 25, 2006||Corning Incorporated||Methods of manufacturing glass sheets with reduced blisters|
|US7358205||Sep 1, 2004||Apr 15, 2008||Nippon Electric Glass Co., Ltd.||Alkali-free glass substrate|
|US7475568||Apr 27, 2005||Jan 13, 2009||Corning Incorporated||Method of fining glass|
|US7534734 *||Nov 13, 2006||May 19, 2009||Corning Incorporated||Alkali-free glasses containing iron and tin as fining agents|
|US7628039||Feb 5, 2009||Dec 8, 2009||Corning Incorporated||System and method for controlling the environmental around one or more vessels in a glass manufacturing system|
|US7696113 *||Dec 1, 2008||Apr 13, 2010||Corning Incorporated||Method of manufacturing alkali-free glasses containing iron and tin as fining agents|
|US7851394||Jun 28, 2006||Dec 14, 2010||Corning Incorporated||Fining of boroalumino silicate glasses|
|US7935649||Apr 8, 2010||May 3, 2011||Corning Incorporated||Alkali-free glasses containing iron and tin as fining agents|
|US8127572 *||Feb 23, 2011||Mar 6, 2012||Corning Incorporated||Method of eliminating blisters in a glass making process|
|US8158543||Feb 25, 2009||Apr 17, 2012||Corning Incorporated||Fining agents for silicate glasses|
|US8623776||Jun 19, 2013||Jan 7, 2014||Corning Incorporated||Silicate glasses having low seed concentration|
|US8640498||Dec 10, 2010||Feb 4, 2014||Corning Incorporated||Fining of boroalumino silicate glasses|
|US8642491||Dec 10, 2010||Feb 4, 2014||Corning Incorporated||Fining of boroalumino silicate glasses|
|US8753993||Nov 1, 2012||Jun 17, 2014||Corning Incorporated||Glass compositions having high thermal and chemical stability and methods of making thereof|
|US8763429||Nov 10, 2010||Jul 1, 2014||Corning Incorporated||Glass compositions having high thermal and chemical stability and methods of making thereof|
|US9073779||Jan 2, 2014||Jul 7, 2015||Corning Incorporated||Fining agents for silicate glasses|
|US9346705||Aug 13, 2014||May 24, 2016||Corning Incorporated||Intermediate to high CTE glasses and glass articles comprising the same|
|US9388064||Jul 30, 2009||Jul 12, 2016||Nippon Electric Glass Co., Ltd.||Tempered glass and manufacturing method for the same|
|US9475720||Nov 26, 2012||Oct 25, 2016||Corning Incorporated||System and method for restricting inward hydrogen permeation in a glass manufacturing system|
|US20020193232 *||Mar 7, 2002||Dec 19, 2002||Asahi Glass Company, Limited||Process for producing a glass for cathode ray tubes|
|US20030007772 *||Jun 25, 2002||Jan 9, 2003||Borrelli Nicholas F.||Method of making optical fiber devices and devices thereof|
|US20040038798 *||Sep 2, 2003||Feb 26, 2004||Nippon Electric Glass Co., Ltd.||CRT funnel of a non beam-index type|
|US20040091222 *||Jan 18, 2002||May 13, 2004||John Canning||Optical fibre|
|US20040177649 *||Mar 13, 2003||Sep 16, 2004||Corning Incorporated||Methods of manufacturing glass sheets with reduced blisters|
|US20040263849 *||Jun 24, 2003||Dec 30, 2004||Becken Keith J.||Methods for quantifying the oxidation state of glass|
|US20050025445 *||Jul 31, 2003||Feb 3, 2005||Schoroeder Joseph F.||Method of making at least one hole in a transparent body and devices made by this method|
|US20050050923 *||Sep 4, 2003||Mar 10, 2005||Grzesik Paul R.||System and method for suppressing the formation of oxygen inclusions and surface blisters in glass sheets and the resulting glass sheets|
|US20050065014 *||Sep 1, 2004||Mar 24, 2005||Toshiharu Narita||Alkali-free glass substrate|
|US20060086146 *||Nov 18, 2005||Apr 27, 2006||Grzesik Paul R||System and method for suppressing the formation of oxygen inclusions and surface blisters in glass sheets and the resulting glass sheets|
|US20060242995 *||Apr 27, 2005||Nov 2, 2006||Bookbinder Andrea W||Method of fining glass|
|US20060242996 *||Apr 27, 2005||Nov 2, 2006||Gilbert Deangelis||System and method for controlling the environment around one or more vessels in a glass manufacturing system|
|US20060293162 *||Jun 28, 2006||Dec 28, 2006||Ellison Adam J||Fining of boroalumino silicate glasses|
|US20070149380 *||Dec 8, 2006||Jun 28, 2007||Dorfeld William G||Method of eliminating blisters in a glass making process|
|US20080047300 *||Oct 12, 2007||Feb 28, 2008||Rhoads Randy L||Defect reduction in manufacture glass sheets by fusion process|
|US20080110208 *||Nov 13, 2006||May 15, 2008||Adam James Gillmar Ellison||Alkali-free glasses containing iron and tin as fining agents|
|US20080127679 *||Jan 4, 2008||Jun 5, 2008||Asahi Glass Company, Limited||Process for producing alkali free glass and alkali free glass plate|
|US20090133441 *||Dec 1, 2008||May 28, 2009||Adam James Gillmar Ellison||Method of manufacturing alkali-free glasses containing iron and tin as fining agents|
|US20090215607 *||Feb 25, 2009||Aug 27, 2009||Matthew John Dejneka||Fining agents for silicate glasses|
|US20090241602 *||Feb 5, 2009||Oct 1, 2009||Gilbert Deangelis||System and method for controlling the environmental around one or more vessels in a glass manufacturing system|
|US20090325776 *||Jul 30, 2009||Dec 31, 2009||Nippon Electric Glass Co., Ltd.||Tempered glass and manufacturing method for the same|
|US20100192633 *||Oct 23, 2009||Aug 5, 2010||Gilbert Deangelis||System and method for controlling the environment around one or more vessels in a glass manufacturing system|
|US20100288361 *||May 7, 2010||Nov 18, 2010||Eveline Rudigier-Voigt||Thin-film solar cell and process for producing a thin-film solar cell|
|US20110048074 *||Nov 10, 2010||Mar 3, 2011||Danielson Paul S||Glass compositions having high thermal and chemical stability and methods of making thereof|
|US20110079049 *||Dec 10, 2010||Apr 7, 2011||Ellison Adam J G||Fining of boroalumino silicate glasses|
|US20110082022 *||Dec 10, 2010||Apr 7, 2011||Ellison Adam J G||Fining of boroalumino silicate glasses|
|US20110138858 *||Feb 23, 2011||Jun 16, 2011||William Gurney Dorfeld||Method of eliminating blisters in a glass making process|
|US20130045386 *||Oct 12, 2012||Feb 21, 2013||Nippon Electric Glass Co., Ltd.||Tempered glass and manufacturing method for the same|
|US20140152914 *||Nov 26, 2013||Jun 5, 2014||Corning Incorporated||Low-Fe Glass for IR Touch Screen Applications|
|CN100515969C||Feb 26, 2004||Jul 22, 2009||康宁股份有限公司||Methods of manufacturing glass sheets with less blisters|
|CN101326129B||Dec 8, 2006||Jun 22, 2011||康宁股份有限公司||Method of eliminating blisters in a glass making process|
|DE102005039377A1 *||Aug 19, 2005||Feb 22, 2007||Schott Ag||Production of aluminosilicate float glass for flat display screens, especially TFT displays, involves purifying the melt before floating, using a combination of arsenic-III oxide and tin-IV oxide|
|EP1227068A1 *||Dec 11, 2001||Jul 31, 2002||NIPPON ELECTRIC GLASS COMPANY, Limited||Crt funnel of a non beam-index type|
|EP1321442A1 *||Nov 26, 2002||Jun 25, 2003||Corning Incorporated||High strain point glasses|
|EP1698596A1 *||Dec 21, 2004||Sep 6, 2006||Nippon Electric Glass Co., Ltd.||Production apparatus for borosilicate sheet glass article, production process therefor and borosilicate sheet glass article|
|EP1698596A4 *||Dec 21, 2004||Mar 7, 2012||Nippon Electric Glass Co||Production apparatus for borosilicate sheet glass article, production process therefor and borosilicate sheet glass article|
|EP2484645A2||Nov 13, 2007||Aug 8, 2012||Corning Incorporated||Alkali-free glasses containing iron and tin as fining agents|
|WO2004083134A1 *||Feb 26, 2004||Sep 30, 2004||Corning Incorporated||Methods of manufacturing glass sheets with reduced blisters|
|WO2013020128A1||Aug 6, 2012||Feb 7, 2013||Corning Incorporated||Photovoltaic module package|
|WO2014179140A2||Apr 24, 2014||Nov 6, 2014||Corning Incorporated||Photovoltaic module package|
|WO2015023561A2||Aug 11, 2014||Feb 19, 2015||Corning Incorporated||Intermediate to high cte glasses and glass articles comprising the same|
|WO2015038841A2||Sep 12, 2014||Mar 19, 2015||Corning Incorporated||Ion exchangeable glasses with high crack initiation threshold|
|WO2016053775A1 *||Sep 25, 2015||Apr 7, 2016||Corning Incorporated||Methods and glass manufacturing system for impacting compaction in a glass sheet|
|WO2016069821A1||Oct 29, 2015||May 6, 2016||Corning Incorporated||Dimensionally stable fast etching glasses|
|U.S. Classification||65/90, 65/134.9, 65/134.1, 65/193|
|International Classification||G02F1/1333, C03B5/225, C03C3/11, C03B17/06, C03C3/091, C03C1/00|
|Cooperative Classification||C03C1/004, C03C3/091, C03B17/06|
|European Classification||C03C3/091, C03C1/00C, C03B17/06|
|Mar 29, 2004||FPAY||Fee payment|
Year of fee payment: 4
|Apr 10, 2008||FPAY||Fee payment|
Year of fee payment: 8
|Apr 21, 2008||REMI||Maintenance fee reminder mailed|
|Apr 10, 2012||FPAY||Fee payment|
Year of fee payment: 12